NZ553938A - Photovoltaic cell - Google Patents

Photovoltaic cell

Info

Publication number
NZ553938A
NZ553938A NZ553938A NZ55393805A NZ553938A NZ 553938 A NZ553938 A NZ 553938A NZ 553938 A NZ553938 A NZ 553938A NZ 55393805 A NZ55393805 A NZ 55393805A NZ 553938 A NZ553938 A NZ 553938A
Authority
NZ
New Zealand
Prior art keywords
layer
semiconductor material
photovoltaic cell
doped semiconductor
process according
Prior art date
Application number
NZ553938A
Inventor
Hans-Josef Sterzel
Original Assignee
Basf Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Ag filed Critical Basf Ag
Publication of NZ553938A publication Critical patent/NZ553938A/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03925—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIIBVI compound materials, e.g. CdTe, CdS
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Manufacturing & Machinery (AREA)
  • Photovoltaic Devices (AREA)
  • Silicon Compounds (AREA)

Abstract

Disclosed is a photovoltaic cell comprising a photovoltaically active semiconductor of the formula (Zn1-xMnxTe)1-y(SiaTeb)y, where x is from 0.01 to 0.99, y is from 0.01 to 0.2, a is from 1 to 2, and b is from 1 to 3, and a process for producing the photovoltaic cell.

Description

New Zealand Paient Spedficaiion for Paient Number 553938 553938 PF 0000055978/SB "as originally filed" Photovoltaic cell Description The invention relates to photovoltaic cells and the photovoltaically active semiconductor material present therein.
Photovoltaically active materials are semiconductors which convert light into electric energy. The principles of this have been known for a long time and are utilized industrially. Most of the solar cells used industrially are based on crystalline silicon (single-crystal or polycrystalline). In a boundary layer between p- and n-conducting silicon, incident photons excite electrons of the semiconductor 15 so that they are raised from the valence band to the conduction band.
The magnitude of the energy gap between the valence band and the conduction band limits the maximum possible efficiency of the solar cell. In the case of silicon, this is about 30% on irradiation with sunlight. In contrast, an efficiency of 20 about 15% is achieved in practice because some of the charge carriers recombine by various processes or deactivate by further mechanisms and are thus no longer effective.
DE 102 23 744 A1 discloses alternative photovoltaically active materials and 25 photovoltaic cells in which these are present, which have the loss mechanisms which reduce efficiency to a lesser extent.
With an energy gap of about 1.1 eV, silicon has quite a good value for practical use. A decrease in the energy gap will push more charge carriers into the 30 conduction band, but the cell voltage becomes lower. Analogously, larger energy gaps would result in higher cell voltages, but because fewer photons are available to be excited, lower usable currents are produced.
Many arrangements such as series arrangement of semiconductors having different 35 energy gaps in tandem cells have been proposed in order to achieve higher J" .» r - 553938 $ PF0000055978/SB efficiencies. However, these are very difficult to realize economically because of their complicated structure.
A new concept comprises generating an intermediate level within the energy gap 5 (up-conversion). This concept is described, for example, in Proceedings of the 14th Workshop on Quantum Solar Energy Conversion-Quantasol 2002, March 17-23, 2002, Rauris, Salzburg, Austria, "Improving solar cells efficiencies by the up-conversion", Tl. Trupke, M.A. Green, P. Wtirfel or "Increasing the Efficiency of Ideal Solar Cells by Photon Induced Transitions at intermediate Levels", A. Luque ( 10 and A. Marti, Phys. Rev. Letters, Vol. 78, No. 26, June 1997, 5014-5017. In the case of a band gap of 1.995 eV and an energy of the intermediate level of 0.713 eV, the maximum efficiency is calculated to be 63.17%.
Such intermediate levels have been confirmed spectroscopically, for example in 15 the system Cdi.yMnyOxTei.x or Zni-xMnxOyTei.y. This is described in "Band anticrossing in group II-OxVli_x highly mismatched alloys: Cdi-yMnyOxTei_x quaternaries synthesized by O ion implantation", W. Walukiewicz et al., Appl. Phys. Letters, Vol 80, No. 9, March 2002, 1571-1573, and in "Synthesis and optical properties of II-O-VI highly mismatched alloys", W, Walukiewicz et al., 20 Appl. Phys. Vol 95, No. 11, June 2004, 6232-6238. According to these authors, the desired intermediate energy level in the band gap is raised by part of the tellurium anions in the anion lattice being replaced by the significantly more electronegative ' oxygen ion. Here, tellurium was replaced by oxygen by means of ion implantation in thin films. A significant disadvantage of this class of materials is that the 25 solubility of oxygen in the semiconductor is extremely low. This results in, for example, the compounds Zni„xMnxTei_yOy in which y is greater than 0.001 being thermodynamically unstable. On irradiation over a prolonged period, they decompose into the stable tellurides and oxides. Replacement of up to 10 atom% of tellurium by oxygen would be desirable, but such compounds are not stable.
Zinc telluride, which has a direct band gap of 2.32 eV at room temperature, would be an ideal semiconductor for the intermediate level technology because of this large band gap. Zinc in zinc telluride can readily be replaced continuously by manganese, with the band gap increasing to about 2.8 eV for MnTe ("Optical 35 Properties of epitaxial ZnMnTe and ZnMgTe films for a wide range of alloy 553938 compositions", X. Liu et al, J. Appl. Phys. Vol. 91, No. 5, March 2002, 2859-2865; "Bandgap of Zni.xMnxTe: non linear dependence on composition and temperature", H.C. Mertins etal., Semicond. Sci. Technol. 8 (1993) 1634-1638).
Zni.xMnxTe can be doped with up to 0.2 mol% of phosphorus to make it p-conductive, with an electrical conductivity in the range from 10 to 30 ST'cm"1 ("Electrical and Magnetic Properties of Phosphorus Doped Bulk Zni.xMnxTe", Le Van Khoi et al., Moldavian Journal of Physical Sciences, No. 1, 2002, 11-14). Partial replacement of zinc by aluminum gives n-conductive species ("Aluminium-10 doped n-type ZnTe layers grown by molecular-beam epitaxy", J.H. Chang et al., Appl. Phys. Letters, Vol 79, No. 6, August 2001, 785-787; "Aluminium doping of ZnTe grown by MOPVE", S.I. Gheyas et al., Appl. Surface Science 100/101 (1996) 634-638; "Electrical Transport and Photoelectronic Properties of ZnTe: Al Crystals", T.L. Lavsen et al., J. Appl. Phys., Vol 43, No. 1, Jan 1972, 172-182). At 15 degrees of doping of about 4*1018 Al/cm3, electrical conductivities of from about 50 to 60 Q^cirf1 can be achieved.
It is an object of the present invention to provide a photovoltaic cell which has a high efficiency and a high electric power and avoids the disadvantages of the prior art. A further object of the present invention is to provide, in particular, a photovoltaic cell comprising a thermodynamieally stable photovoltaically active semiconductor material which has an intermediate level in the energy gap. The above objects should be read disjunctively with the object of at least providing a useful alternative.
This object is achieved according to the invention by a photovoltaic cell comprising a photovoltaically active semiconductor material, wherein the photovoltaically active semiconductor material is a p- or n-doped semiconductor material comprising mixed compounds of the formula (I): (Zni .xMnxT e)i.y(SiaT eb)y (I) where x is from 0.01 to 0.99, 35 y is from 0.001 to 0.2, a is from 1 to 2 and b is from 1 to 3.
INTELLECTUAL PROPERTY OFFICE OF N.Z. -9 JUL 2009 received 553938 PF 0000055978/SB The object of the invention is thus surprisingly achieved completely differently than would be expected from the references cited. To produce intermediate levels in the energy gap, the tellurium is not replaced by a significantly more 5 electronegative element but instead silicon is introduced into the semiconductor material having the formula Zni_xMnxTe. This is surprising since the electronegativity of silicon is 1.9 and thus differs only slightly from that of tellurium, viz. 2.1.
The variable x can be from 0.01 to 0.99, and y can be from 0.001 to 0.2, preferably from 0.005 to 0.1. The variable a can be from 1 to 2, and b can be from 1 to 3. Preference is given to a = 2 andb = 3, which gives the stoichiometry Si2Te3.
The photovoltaic cell of the invention has the advantage that the photovoltaically 15 active semiconductor material used is thermodynamically stable even after introduction of silicon telluride. Furthermore, the photovoltaic cell of the invention has a high efficiency (up to 60%), since the silicon telluride produces intermediate levels in the energy gap of the photovoltaically active semiconductor material. Without an intermediate level, only photons having at least the energy of the 20 energy gap could raise electrons or charge carriers from the valence band into the conduction band. Photons having a higher energy also contribute to the efficiency, with the excess energy compared to the band gap being lost as heat. In the case of an intermediate level which is present in the semiconductor material used according to the present invention and can be partly occupied, more photons can 25 contribute to excitation.
The photovoltaic cell of the invention comprises a p-doped semiconductor material and an n-doped semiconductor material, with these two semiconductor materials being adjoined so as to form a p-n transition. Both the p-doped semiconductor 30 material and the n-doped semiconductor material comprise substantially mixed compounds of the formula (I), with the material additionally being doped with donor ions in the p-doped semiconductor material and acceptor ions in the n-doped semiconductor material. 553938 PF 0000055978/SB The p-doped semiconductor material preferably contains at least one element from the group consisting of As and P at au atomic concentration of up to 0.1 atom% and the n-doped semiconductor material preferably contains at least one element from the group consisting of Al, In and Ga at an atomic concentration of up to 5 0.5 atom%. Preferred doping elements are aluminum and phosphorus. hi a preferred embodiment of the photovoltaic cell of the invention, it comprises a substrate, in particular an electrically conductive substrate, a p layer of the p-doped semiconductor material having a thickness of from 0.1 to 10 (J,m, preferably from 10 0.3 to 3 Jim, and an n layer of the n-doped semiconductor material having a thickness of from 0.1 to 10 pm, preferably from 0.3 to 3 ji.m. The substrate is preferably a flexible metal foil or a flexible metal sheet. The combination of a flexible substrate with thin photovoltaically active layers gives the advantage that no complicated and thus expensive support has to be used for holding the solar 15 module comprising the photovoltaic cells of the invention. In the case of nonflexible substrates such as glass or silicon, wind forces have to be dissipated by means of complicated support constructions in order to avoid breakage of the solar module. On the other hand, if deformation due to flexibility is possible, very simple and inexpensive support constructions which do not have to be rigid under 20 deformation forces can be used. In particular, a stainless steel sheet is used as preferred flexible substrate for the purposes of the present invention.
The invention further provides a process for producing a photovoltaic cell according to the invention, which comprises coating a substrate with at least one 25 layer of the p-doped semiconductor material and at least one layer of the n-doped semiconductor material, with the layers having a thickness of from 0.1 to 10 |im, preferably from 0.3 to 3 |xm.
Coating of the substrate with the p or n layer preferably comprises at least one 30 deposition process selected from the group consisting of sputtering, laser ablation, electrochemical deposition or electroless deposition. The previously p- or n-doped semiconductor material comprising mixed compounds of the formula (T) can be applied as a layer to the substrate by means of the respective deposition process. As an alternative thereto, a layer of the semiconductor material without p- or n-35 doping can firstly be produced by means of the deposition process and this layer 553938 PF 0000055978/SB - 6 — can subsequently be p- or n-doped. The introduction according to the invention of silicon in the form of silicon telluride (if the respective layer produced by one of the abovementioned deposition processes does not yet have the appropriate structure) is preferably carried out subsequent to the deposition process (and, if 5 appropriate, to the p- or n-doping).
One possible deposition process is coating by sputtering. The term sputtering refers to the ejection of atoms from a sputtering target serving as electrode by means of accelerated ions and deposition of the ejected material on a substrate (e.g. stainless 10 steel). To coat a substrate according to the present invention, sputtering targets comprising zinc, manganese, tellurium and silicon, for example, are produced by melting together the constituents for sputtering or the individual constituents of the semiconductor material are sputtered onto the substrate in succession and subsequently heated to a temperature of from 400 to 900°C.
Preference is given to using zinc, manganese, tellurium and silicon having a purity of at least 99.5% for producing the sputtering target. Zinc, manganese, tellurium and silicon telluride (SiaTeb) are, for example, melted under reduced pressure at temperatures of from 1200 to 1400°C in a dewatered fused silica tube. Doping 20 elements for p- or n-doping are preferably introduced into the sputtering target during production of the sputtering target The doping elements, preferably aluminum for n conduction and phosphorus for p conduction, are accordingly introduced at the beginning into the sputtering target. The compounds AITe and ZJI3P2 are so thermally stable that they survive the sputtering process without any 25 significant change in stoichiometry. A layer having one doping is then firstly sputtered onto the substrate and a second layer having the opposite doping is sputtered directly thereon.
A further preferred embodiment of a deposition process which can be used 30 according to the invention is electrochemical deposition of Zni_xMnxTe on the electrically conductive substrate. The electrochemical deposition of ZnTe is described in "Thin films of ZnTe electrodeposited on stainless steel", A.E. Rakhsan and B. Pradup, Appl. Phys. A (2003), Pub online Dec. 19, 2003, Springer-Verlag; "Electrodeposition of ZnTe for photovoltaic alls", B. Bozzini et 35 al., Thin Solid Films, 361-362, (2000) 288-295; Electrochemical deposition of PF 0000055978/SB 553938 ZnTe Thin films", T. Mahalingam et al., Semicond. Sci. Technol. 17 (2002) 469-470; "Electrodeposition of Zn-Te Semiconductor Film from Acidic Aqueous Solution", R. Ichino et al., Second Internal. Conference on Processing Materials for Properties, The Minerals, Metals & Materials Society, 2000, and in US patent 5 4,950,615, but not the electrochemical deposition of mixed Za/Mn/Te layers.
A process according to the invention can also comprise electroless deposition of 2ni_xMnxTe layers by crosslinking an aqueous solution comprising Zn2+, Mn2+ and Te03 " ions by means of hypophosphorous acid (H3PO2) as reducing agent at 10 temperatures of from 30 to 90°C in the presence of the substrate. The hypophosphorous acid reduces Te032" to Te2'. Deposition on electrically nonconductive substrates is also made possible in this way.
Depending on the deposition process, after-treatments to incorporate silicon 15 telluride into the layers and sometimes also to introduce the dopants may be necessary.
In a preferred embodiment of the present invention, the process of the invention comprises the following process steps: a) coating of the substrate with a first layer of Zn i xMnxTc, b) introduction of silicon into the first layer to produce mixed compounds of the formula (I), c) establishment of p- or n-doping with donor atoms or acceptor atoms, 25 d) coating of the first layer with a second layer of Zni_JVLnxTe, e) introduction of silicon into the second layer to produce mixed compounds of the formula (I), f) establishment of n- or p-doping with acceptor atoms or donor atoms and g) application of an electrically conductive transparent layer and a protective 30 layer to the second layer.
In step a), the electrically conductive substrate is coated with a first layer of Zni_xMnxTe by, for example, sputtering, electrochemical deposition or electroless deposition. The substrate is preferably a metal sheet or a metal foil. 553938 PF 0000055978/SB 8- Silicon is then introduced into this first layer in step b) to produce mixed compounds of the formula (I). The introduction of silicon is effected, for example, by applying Si2Te3 to the first layer by sputtering and subsequently carrying out a cocrystallization by means of a thermal after-treatment at from 600 to 1200°C, 5 preferably from 800 to 1000°C, so as to obtain the desired composition.
In step c), the establishment of p- or n-doping is subsequently effected by doping with donor atoms or acceptor atoms. For example, the first layer is doped either with phosphorus (for example from PCI3) to form a p conductor or with aluminum (. : 10 (for example from AICI3) to form an n conductor.
In step d), the second layer of Zni_xMnxTe is then deposited on the first layer. For this purpose, it is possible, for example, to employ the same deposition process as in step a).
In step e), silicon is introduced into the second layer as described for the first layer in step b).
The doping established in step f) is opposite to the doping established in step c), so 20 that one layer is p-doped and the other layer is n-doped.
^ Finally, an electrically conductive transparent layer and a protective layer are ' applied to the second layer in step g). The electrically conductive transparent layer can be, for example, a layer of indium-tin oxide or aluminum-zinc oxide. 25 Furthermore, it preferably has conductor tracks for establishing electrical contacts on the photovoltaic cell of the invention. The protective layer can, for example, be a layer of SiOx which is preferably applied by CVD or PVD. It is possible, for example, for a layer of a material which is produced in the prior art for films which keep in aromas (e.g. coffee packaging) to serve as protective layer.
Example 1 In accordance with the stoichiometry (Zno.5Mno.5Te)o.95(Si2Te3)o.o5 , PF 0000055978/SB 553938 1.0350 g of Zn; 0.8669 g of Mn; 4.0407 g of tellurium and 0.7316 g of Si2Te3 were weighed into a fused silica tube having an internal diameter of 11 mm and a length of about 15 cm. The SizTeg was prepared separately beforehand by reacting silicon 5 and tellurium at 1000°C in an evacuated fused silica tube. The tube was heated at 300°C under reduced pressure for 10 minutes to effect dewateriiig and then flame sealed at a pressure of less than 0.1 mbar. The tube was heated to 1300°C at 300°C/h in a furnace, the temperature was maintained at 1300°C for 10 hours and the furnace was then allowed to cool. During the 10 hours at 1300°C, the furnace 10 was tilted about its longitudinal axis 30 times per hour by means of a drive in order to mix the melt in the fused silica tube.
After cooling, the fused silica tube was opened and the solidified melt was removed. The excitation levels of the material were determined by means of 15 reflection spectroscopy. Besides the band gap of about 2.3 eV, energy levels at 0.66 eV; 0.76 eV and 0.9 eV were also found.
To produce a photovoltaic cell according to the invention, this material is sputtered onto a substrate.
Example 2 To effect electrochemical deposition, electrolyses were carried out in a 500 ml glass flange vessel provided with double wall, internal thermometer and bottom 25 outlet valve. A stainless steel sheet (100 X 70 X 0.5) was used as cathode. The anode comprised MKUSF04 (graphite). a) Preparation of ZnTe 21.35 g of ZnS04-7H2O and 55.4 mg of Na2Te03 were dissolved in distilled water. This solution was brought to a pH of 2 by means of H2SO4 (2 mol/1) and subsequently made up to 500 ml with distilled water (Zn = 0.15 mol/1; Te = 0.5 rnmol/1; Zn/Te = 300/1). The electrolyte solution was subsequently placed in the electrolysis cell and heated to 80°C. The electrolysis was carried out over a 35 period of 30 minutes at a current of 100.0 mA without stirring. Deposition was

Claims (14)

PF 0000055978/SB 553938 - 10- effected at a cathode area of -50 cm2 (2 mA/cm2). After the electrolysis was complete, the cathode was taken out, rinsed with distilled water and dried. A copper-colored film had been deposited (18.6 mg). 5 b) Preparation of Zni_xMnxTe 21.55 g of ZnS04-7H20 (0.15 mol/1), 47.68 g of MnS04-H20 (0.6 mol/1), 33 g of (NH4)2S04 (0.5 mol/1), 1 g of tartaric acid and 55.4 mg of Na2Te03 (0.5 Eomol/1) were dissolved in distilled water. This solution was brought to a pH of 2 by means ( 10 of H2SO4 (2 mol/1) and made up to 500 ml with distilled water (Zn/Mn/Te = 300/1200/1). The electrolysis solution was subsequently placed in the electrolysis cell and heated to 80°C. The electrolysis was carried out over a period of 60 minutes at a current of 101.3 mA without stirring. Deposition was effected at a cathode area of -50 cm2 (~2 mA/cm2). After the electrolysis was complete, the 15 cathode was taken out, rinsed with distilled water and dried. The weight gain was 26.9 mg. The deposit had a deep dark brown color. ( 553938 -11- Claims:
1. A photovoltaic cell comprising a photovoltaically active semiconductor material, wherein the photovoltaically active semiconductor material is a p-or n-doped semiconductor material including mixed compounds of the formula (I): (Zn1^MnxTe)1_y(SiaTeb)y (T) where x is from 0.01 to 0.99, y is from 0.01 to 0.2, a is from 1 to 2 and b is from 1 to 3.
2. The photovoltaic cell according to claim 1, wherein the p-doped semiconductor material contains at least one element from the group consisting of As and P at an atomic concentration of up to 0.1 atom% and the n-doped semiconductor material contains at least one element from the group consisting of Al, In and Ga at an atomic concentration of up to 0.5 atom%.
3. The photovoltaic cell according to either claim 1 or 2 including a substrate, a p layer of the p-doped semiconductor material having a thickness of from 0.1 to 10 urn and an n layer of the n-doped semiconductor material having a thickness of from 0.1 to 10 urn.
4. The photovoltaic cell according to claim 3, wherein the substrate is a flexible metal foil or a flexible metal sheet. 553938 - 12 -
5. A process for producing a photovoltaic cell according to any one of claims 1 to 4, wherein a substrate is coated with at least one layer of the p-doped semiconductor material and at least one layer of the n-doped semiconductor material, with the layers having a thickness of from 0.1 to 10 |^m. 5
6. The process according to claim 5, wherein the coating process comprises at least one deposition process from the group consisting of sputtering, laser ablation, electrochemical deposition and electroless deposition. 10
7. The process according to claim 6, wherein a sputtering target comprising zinc, manganese, tellurium and silicon is produced by melting together constituents for sputtering.
8. The process according to claim 7, wherein Zn, Mn, Te and Si having a 15 purity of at least 99.5% are used for producing the sputtering target and Zn, Mn, Te and SiaTeb are melted at temperatures of from 1200 to 1400°C under reduced pressure in a dewatered fused silica tube.
9. The process according to either claim 7 or 8, wherein doping elements for 20 p- or n-doping are introduced into the sputtering target during production of the sputtering target.
10. The process according to claim 6, wherein electroless deposition is effected by crosslinking an aqueous solution comprising Zn2+, Mn2+ and TeC>32+ 25 ions by means of hyperphosphorous acid H3PO2 as reducing agent at a temperature of from 30 to 90°C in the presence of the substrate. 30
11. The process according to any one of claims 6 to 10 which comprises the process steps: a) coating of the substrate with a first layer of Zni.xMnxTe, b) introduction of Si into the first layer to produce mixed compounds of the formula (I), 553938 « - 13 - c) establishment of p- or n-doping with donor atoms or acceptor atoms, d) coating of the first layer with a second layer of Zm.xMnxTe, e) introduction of silicon into the second layer to produce mixed compounds of the formula (I), f) establishment of n- or p-doping with acceptor atoms or donor atoms and g) application of an electrically conductive transparent layer and a protective layer to the second layer.
12. A photovoltaic cell produced by a process according to any one of claims 5 to 11.
13. A photovoltaic cell according to claim 1 or claim 12, substantially as herein 15 described with reference to Example 1 and/or Example 2.
14. A process according to claim 5, substantially as herein described with reference to Example 1 and/or Example 2. 10
NZ553938A 2004-10-26 2005-10-25 Photovoltaic cell NZ553938A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004052014A DE102004052014A1 (en) 2004-10-26 2004-10-26 Photovoltaic cell
PCT/EP2005/011433 WO2006045588A1 (en) 2004-10-26 2005-10-25 Photovoltaic cell

Publications (1)

Publication Number Publication Date
NZ553938A true NZ553938A (en) 2009-08-28

Family

ID=35505001

Family Applications (1)

Application Number Title Priority Date Filing Date
NZ553938A NZ553938A (en) 2004-10-26 2005-10-25 Photovoltaic cell

Country Status (11)

Country Link
US (1) US20090133744A1 (en)
EP (1) EP1807873A1 (en)
JP (1) JP2008518448A (en)
KR (1) KR20070084519A (en)
CN (1) CN101048876A (en)
AU (1) AU2005298825A1 (en)
CA (1) CA2582253A1 (en)
DE (1) DE102004052014A1 (en)
NZ (1) NZ553938A (en)
TW (1) TW200631189A (en)
WO (1) WO2006045588A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011131801A1 (en) * 2010-04-22 2011-10-27 Bermudez Benito Veronica Semiconductor material to be used as an active/absorbent layer in photovoltaic devices, method for preparing said active layer, and photovoltaic cell incorporating said layer

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3372997A (en) * 1966-12-22 1968-03-12 Du Pont Ternary copper, zinc, cadmium and manganese dichalcogenides having the pyrite-type crystal structure
WO2002081789A1 (en) * 2001-04-04 2002-10-17 Nikko Materials Co., Ltd. METHOD FOR MANUFACTURING ZnTe COMPOUND SEMICONDUCTOR SINGLE CRYSTAL ZNTE COMPOUND SEMICONDUCTOR SINGLE CRYSTAL, AND SEMICONDUCTOR DEVICE
JP2003179243A (en) * 2001-08-31 2003-06-27 Basf Ag Photovoltaic cell active material and cell containing the same

Also Published As

Publication number Publication date
CN101048876A (en) 2007-10-03
JP2008518448A (en) 2008-05-29
CA2582253A1 (en) 2006-05-04
DE102004052014A1 (en) 2006-05-04
TW200631189A (en) 2006-09-01
WO2006045588A1 (en) 2006-05-04
EP1807873A1 (en) 2007-07-18
KR20070084519A (en) 2007-08-24
AU2005298825A1 (en) 2006-05-04
US20090133744A1 (en) 2009-05-28

Similar Documents

Publication Publication Date Title
Lin et al. Preparation of Cu2ZnSnS4 (CZTS) sputtering target and its application to the fabrication of CZTS thin-film solar cells
Ennaoui et al. Cu2ZnSnS4 thin film solar cells from electroplated precursors: Novel low-cost perspective
Paudel et al. Current enhancement of CdTe-based solar cells
US20080163928A1 (en) Photovoltaic Cell Containing a Semiconductor Photovoltaically Active Material
KR101407805B1 (en) Photovoltaically active semiconductor material and photovoltaic cell
Marchionna et al. Cu2ZnSnS4 solar cells grown by sulphurisation of sputtered metal precursors
US7763794B2 (en) Heterojunction photovoltaic cell
WO2012177804A2 (en) IMPROVED CdTe DEVICES AND METHOD OF MANUFACTURING SAME
KR101312202B1 (en) Photovoltaic cell comprising a photovoltaically active semi-conductor material contained therein
Yuzawa et al. ZnSnP2 thin-film solar cell prepared by phosphidation method under optimized Zn/Sn atomic ratio of its absorbing layer
CN103194722B (en) Manufacture the method for solar cell
CA2585166C (en) Photovoltaic cell comprising a photovoltaically active semiconductor material
Shah et al. A Deep Dive into Cu2ZnSnS4 (CZTS) Solar Cells: A Review of Exploring Roadblocks, Breakthroughs, and Shaping the Future
NZ553938A (en) Photovoltaic cell
Meng et al. Growth of Zn1− xMgxO films with single wurtzite structure by MOCVD process and their application to Cu (InGa)(SSe) 2 solar cells
Romeo CdTe and CuInGaSe 2 Thin-Film Solar Cells
Shigehiro Isomura et al. Preparation of Cu (In1-2 Ga,) Se2 Thin Films by Chemical Spray Pyrolysis
Gessert et al. CdTe devices and method of manufacturing same
Wellings Electrodeposition of semiconductors for applications in thin film solar cells
KR20150108539A (en) Fabrication Method of Solar Cell and Thin-film Solar Cell by using the same

Legal Events

Date Code Title Description
PSEA Patent sealed
ERR Error or correction

Free format text: THE OWNER HAS BEEN CORRECTED TO 3004745, BASF SE, CARL-BOSCH-STRASSE 38, 67056 LUDWIGSHAFEN, DE

Effective date: 20141118